WO2002000546A1 - Reacteur de reformage de combustible et son procede de production - Google Patents
Reacteur de reformage de combustible et son procede de production Download PDFInfo
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- WO2002000546A1 WO2002000546A1 PCT/JP2001/005528 JP0105528W WO0200546A1 WO 2002000546 A1 WO2002000546 A1 WO 2002000546A1 JP 0105528 W JP0105528 W JP 0105528W WO 0200546 A1 WO0200546 A1 WO 0200546A1
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- reformer
- steel material
- fuel
- oxide layer
- fuel reformer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/02—Pretreatment of the material to be coated
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
- C23C8/10—Oxidising
- C23C8/16—Oxidising using oxygen-containing compounds, e.g. water, carbon dioxide
- C23C8/18—Oxidising of ferrous surfaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
- B01J2208/00309—Controlling the temperature by indirect heat exchange with two or more reactions in heat exchange with each other, such as an endothermic reaction in heat exchange with an exothermic reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00504—Controlling the temperature by means of a burner
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/0053—Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/02—Apparatus characterised by their chemically-resistant properties
- B01J2219/025—Apparatus characterised by their chemically-resistant properties characterised by the construction materials of the reactor vessel proper
- B01J2219/0277—Metal based
- B01J2219/0281—Metal oxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0811—Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
- C01B2203/1058—Nickel catalysts
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2240/00—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being
- F01N2240/30—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being a fuel reformer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a fuel reformer and a method for producing the same, and more particularly, to a fuel reformer for reforming a hydrocarbon-based fuel into a hydrogen-rich gas and a method for producing the same.
- the operating temperature of the reformer is about 700 ° C (exit temperature of the reforming catalyst layer). It is estimated that the surface temperature of the material that constitutes the reformer is about 100,000 or more.
- the surface is steam-oxidized to form a rough, porous, and brittle iron oxide layer (considered mainly Fea0a) (hereinafter referred to as a red scale) on the surface, and the red scale is It has a tendency to progress to the inside, There was a problem that the corrosion of the steel material further progressed when the red scale was separated from the substrate. Increasing the thickness of the steel material can reduce the material destruction due to corrosion, but increases the weight, makes it difficult to process, and raises the cost. Was.
- An object of the present invention is to solve the conventional problem, and even when placed in an atmosphere having a low oxygen concentration and / or a high steam concentration at a high temperature, the surface of the steel material constituting the reformer is steam-oxidized to red.
- An object of the present invention is to provide a fuel reformer that is lightweight, inexpensive, inexpensive, reliable, and has a long life without generating scale. Disclosure of the invention
- a fuel reformer according to claim 1 is a fuel reformer for reforming a hydrocarbon-based fuel into a hydrogen-rich gas, and a steel material constituting the reformer.
- a Cr oxide layer is formed on at least a part of the surface.
- the fuel reformer according to claim 2 wherein the Cr oxide layer is formed on a surface of a fuel on a combustion gas flow path side in the fuel reformer according to claim 1. It is characterized by
- the fuel reformer according to claim 3 is the fuel reformer according to claim 1, wherein the Cr oxide layer supplies a mixed gas of the raw fuel for reforming and steam to the reformer. It is characterized in that it is formed on the surface of the mixed gas flow path from the gas to the reforming catalyst filling section.
- the fuel reformer according to claim 4 is the fuel reformer according to claim 1, wherein the Cr oxide layer is formed on a combustion gas flow path side surface of the reformer. It is characterized in that it is formed on the surface of a mixed gas flow path from a fuel supply section that supplies a mixed gas of raw fuel for reforming and steam to the reformer to a charging section of the reforming catalyst.
- the fuel reformer according to claim 5 is the fuel reformer according to claim 1, wherein the average thickness of the Cr oxide layer is 5 to 100 ⁇ m. And features.
- the fuel reformer according to claim 6 is the fuel reformer according to any one of claims 1 to 5, wherein the surface of the steel material constituting the reformer is higher than the Cr concentration of the base material. It is characterized in that a Cr oxide layer formed by forming a thin film having a Cr concentration and then performing a heat treatment is formed.
- Claim 7 forms a Cr oxide layer on the surface of the raw steel material by heat-treating the raw steel material in an oxidizing atmosphere at 600 to 100 ° C.
- a method for manufacturing a fuel reformer comprising manufacturing a reformer using the raw steel material having the Cr oxide layer formed thereon.
- the surface of the raw steel material is heat-treated in an oxidizing atmosphere at 600 to 100 ° C. by heating the fuel reformer manufactured using the raw steel material. Characterized in that a Cr oxide layer is formed on This is a method for manufacturing a fuel reformer.
- a fuel reforming method is characterized in that a Cr oxide layer is formed on the surface of the raw steel material, and a reformer is manufactured using the raw steel material on which the Cr oxide layer is formed. This is the method of manufacturing the porcelain.
- Claim 10 is that after forming a thin film having a Cr concentration higher than the Cr concentration of the base material on the surface of the raw steel material, the fuel reformer manufactured by using the raw steel material is replaced by a 35 A method for producing a fuel reformer, characterized in that a Cr oxide layer is formed on the surface of the raw steel material by heat treatment in an oxidizing atmosphere at 0 to 65 ° C. is there.
- a Cr oxide layer is formed on the surface of the raw steel material by heat treatment in an oxidizing atmosphere at 0 to 65 ° C.
- the Cr oxide layer is formed on at least a part of the surface of the steel material constituting the fuel reformer.
- the C r oxide layer is specifically Ri spinel oxide layer der of F e 0 ⁇ C r 2 0 3 or C r 2 0 3 as a main the C r, the steel material of the underlying at ⁇ tight It has excellent adhesion, has few lattice defects, significantly reduces the diffusion of metal ions and oxygen ions, and prevents steam oxidation. Accordingly, the generation of red scale is suppressed, and the heat resistance is improved, thereby improving the life and reliability of the fuel reformer.
- the Cr oxide layer preferably has an average thickness in the range of 5 to 100 zm.
- the average thickness is 5 to 100 111 and the oxide layer has good adhesion to the surface of the underlying steel material and is dense and resistant to steam oxidation. Is excellent. If the length is less than 5 m, the Cr oxide layer may be partially lost, and a uniform and dense Cr oxide layer may not be formed. It takes a long time to form the refuse, which is uneconomical.
- the surface of the steel material constituting the reformer is coated with a C higher than the Cr concentration of the base material by a method such as squeezing or chrome plating.
- a method such as squeezing or chrome plating.
- heat treatment is performed to form a Cr oxide layer. You. By doing so, the heat treatment temperature can be lowered, so that it is possible to reduce the amount of energy without any trouble and save energy, and the Cr oxide layer formed by the heat treatment becomes dense.
- the raw steel material is heat-treated in an oxidizing atmosphere at 600 to 1000 ° C., so that the surface of the raw steel material is Cr-oxidized.
- a fuel reformer is manufactured using the raw steel material on which the Cr oxide layer is formed.
- the surface of the raw steel material is Fe 0. can and this to form a C r 2 0 3 or spinel oxide layer of C r 2 0 3 as a main the C r.
- the temperature at which the raw steel material is heat-treated is below 800 ° C, a Cr oxide layer may not be formed, and an expensive heater is required to perform the heat treatment above 100 ° C. Therefore, the amount of energy input to the heater also increases, which is uneconomical. Therefore, it is preferable to set the temperature in the range of 600 ° C. to 100 ° C. If the heat treatment time is less than 30 minutes, a uniform and dense Cr oxide layer may not be formed.If the heat treatment time exceeds 10 hours, the amount of energy input for the heat treatment increases, which is uneconomical. . Therefore, the heat treatment time is preferably in the range of 30 minutes to 10 hours.
- the fuel reformer itself manufactured using the raw steel material is heat-treated in an oxidizing atmosphere at 600 to 100 ° C.
- a Cr oxide layer is formed on the surface of the raw steel material.
- the heat treatment of the fuel reformer itself in an oxidizing atmosphere at 600 ° C. to 100 ° C., preferably for 30 minutes to 10 hours, can also be used as a raw material steel.
- a spinel oxide layer of Cr mainly composed of Fe 0 ⁇ Cra 03 or Cr 2 O 3 can be formed on the surface of the material.
- a thin film having a Cr concentration higher than the Cr concentration of the base material is formed on the surface of the raw steel material by a method such as chrome plating or chrome plating. (Chromium alloy thin film, Chromium thin film, etc., average thickness of about 1 to 100 m).
- chrome plating or chrome plating Chromium alloy thin film, Chromium thin film, etc., average thickness of about 1 to 100 m.
- a thin film having a higher Cr concentration than the base material is previously formed on the surface of the steel material constituting the reformer, even if the base material has a low Cr concentration, the surface is dense.
- a simple Cr oxide layer can be formed in a short time. After forming a thin film having a Cr concentration higher than that of the base metal on the surface of the raw steel material, heat treatment was performed in an oxidizing atmosphere at 350 to 650 ° C to form a Cr oxide layer.
- a fuel reformer can be manufactured by assembling or welding with steel materials. The processing temperature is 350 to 650 ° C. If the temperature is lower than 350 ° C, the Cr oxide layer may not be formed, and if it exceeds 650 ° C, the amount of energy also increases, making it uneconomical for the effect. Becomes
- a thin film having a Cr concentration higher than that of the base material (a thin film of a chromium alloy, a thin film of a chromium, etc.) is formed on the surface of the raw steel material.
- the fuel reformer manufactured using this steel material is heat-treated in an oxidizing atmosphere at 350-650 ° C.
- a Cr oxide layer is formed on the surface of the raw steel material. Since the heat treatment is performed in an oxidizing atmosphere at 350 to 650 ° C, no energy is required, the energy amount can be reduced, energy can be saved, and the Cr oxide layer formed by the heat treatment becomes dense.
- a fuel reformer having improved life and reliability can be manufactured by the invention according to the present invention.
- FIG. 1 is an explanatory sectional view of one embodiment of the fuel reformer of the present invention.
- FIG. 2 is an explanatory sectional view of another fuel reformer of the present invention.
- FIG. 3 is an explanatory sectional view of another fuel reformer of the present invention.
- FIG. 1 is an explanatory sectional view of an embodiment of the fuel reformer of the present invention.
- a fuel reformer 1A of the present invention comprises a reforming tube outer tube 2, a reforming tube inner tube 3, a reforming tube inner tube upper plate 4, a reforming tube outer tube upper plate 5, and a reforming tube outer plate 5. It has a raw fuel inlet 6, a reformed gas outlet 7, etc., provided on the cylinder upper plate 5, and a heating unit 8, which introduces combustion gas for heating into a hollow part provided in the center of the reformer. Between the reforming tube 9, the catalyst tube 10 installed inside the reforming tube 9, and the reforming tube inner tube 3 and the catalyst tube 1.0, and on the reforming tube inner tube upper plate 4.
- gas fuel and air are introduced into a parner 15 to burn the gas fuel, and the combustion gas is guided to a heating section 8 through a combustion gas pipe 14 as indicated by a dashed arrow to form a reforming catalyst 1.
- the flue gas is discharged from the flue gas outlet 12 through the space between the reformer tube 2 and the flue gas tube 13.
- a hydrocarbon-based fuel for example, methane
- a hydrocarbon-based fuel for example, methane
- water vapor is introduced into the fuel reformer 1A from the raw fuel inlet 6 as shown by the arrow, and is brought into contact with the heated reforming catalyst 11. Reform.
- the operation temperature of the fuel reformer 1A is controlled to about 700 ° C. (outlet temperature of the reforming catalyst 11).
- about 75% of hydrogen, about 10% of carbon monoxide, and about 10% of carbon dioxide can be obtained.
- the reformed gas containing the remaining methane gas is discharged from the reformed gas outlet 7 through the space between the outer tube 2 of the reforming tube and the catalyst tube 10 as shown by the arrow.
- the fuel reformer 1A is made by heat-treating the raw steel material in an oxidizing atmosphere at 600 ° 100 ° C. for 30 minutes to 10 hours.
- Bold lines such as the combustion gas pipes 14 that constitute 1 A, the flue gas pipes 13, the flue gas outlets 12, the reforming pipe outer cylinder 2, the reforming pipe inner cylinder 3, and the reforming pipe inner cylinder upper plate 4 are shown.
- a Cr oxide layer is formed on the surface of the steel material that composes these parts on the side where the combustion gas contacts and flows.
- the side where the combustion gas flows in contact with the combustion gas at the location indicated by the bold line including the heating section 8 of the fuel reformer 1A is in an atmosphere of high temperature, low oxygen concentration and easy to generate steam oxidation.
- the Cr oxide layer in advance on the gas flow path side surface, water vapor oxidation on the surface is prevented, the generation of red scale is prevented, and heat resistance is improved. You. This will improve the life and reliability of the reformer.
- FIG. 2 is an explanatory sectional view of another fuel reformer of the present invention.
- the fuel reformer 1B of the present invention is used for reforming, such as the upper part of the reforming tube outer cylinder 5, the raw fuel inlet 6, and a part of the upper part of the catalyst tube 10 shown by a thick line.
- the Cr oxide layer is previously formed on a surface of a flow path from which a mixed gas flows and comes into contact, from a fuel supply unit that supplies a mixed gas of raw fuel and steam to a charging unit of the reforming catalyst 11.
- the configuration is the same as that of the fuel reformer 1A shown in FIG.
- the mixed gas flow path from the fuel supply section that supplies the mixed gas to the fuel reformer 1B to the filling section of the reforming catalyst 11 is in an atmosphere where steam oxidation is likely to occur at high temperature and high steam concentration.
- the Cr oxide layer is formed on the surface of the mixed gas flow path, steam oxidation on the surface is prevented, red scale is prevented from being generated, and heat resistance is improved. This will improve the life and reliability of the reformer.
- FIG. 3 is an explanatory sectional view of another fuel reformer of the present invention.
- FIG. 3 a combustion gas pipe 14, a combustion exhaust gas pipe 13, a combustion exhaust gas outlet 12, a reforming pipe outer cylinder 2, a reforming pipe inner cylinder 3, and a reforming pipe inside the fuel reformer 1 C of the present invention are shown.
- the Cr oxide layer is formed on the surface of the steel material that constitutes the side where the combustion gas contacts and flows, such as those indicated by the bold line, such as ⁇ 4 on the cylinder, and the reforming pipe indicated by the bold line. From the fuel supply section that supplies the mixed gas of raw fuel for reforming and steam to the charging section of the reforming catalyst 11, such as the outer cylinder upper plate 5, raw fuel inlet 6, and a part above the catalyst tube 10. Except that the Cr oxide layer is formed on the surface of the mixed gas flow path, the structure is the same as that of the fuel reformers 1A and IB shown in FIGS. 1 and 2.
- the combustion gas flow path including the heating section 8 of the fuel reformer 1 C In a low oxygen concentration atmosphere where steam oxidation is likely to occur, and the mixed gas flow path from the fuel supply unit that supplies the mixed gas to the fuel reformer 1C to the charging unit of the reforming catalyst 11 has a high temperature. And the atmosphere is apt to generate steam oxidation at a high steam concentration, so that the Cr oxide layer is formed on the combustion gas channel side surface and the mixed gas channel surface, so that both surfaces are formed. The oxidation of steam at the surface is prevented, the generation of red scale is prevented, and the heat resistance is improved. This improves the service life and reliability of the reformer.
- the fuel reformer of the present invention is not limited to the fuel reformers of the types shown in FIGS. 1 to 3, but may be, for example, a multi-tube fuel reformer, a flat plate fuel reformer, or the like.
- the reformers described in FIGS. 1 and 3 of Japanese Patent No. 2703831 and the reformers described in FIGS. 2 to 8 of Japanese Patent Application Laid-Open No. 6-13096 are disclosed.
- the reformer, the reformer described in FIGS. 1 to 3 of JP-A-6-56401, and the reformer described in FIGS. 1, 4, and 7 of JP-A-7-109105 The reformer, the reformer described in FIGS. 1 and 3 of JP-A-7-232801, the reformer described in FIG.
- the fuel reformer according to claim 1 of the present invention has a reduced surface area of the steel material constituting the reformer without increasing the thickness of the reformer as in the prior art.
- the Cr oxide layer is formed in advance, so that the steel material constituting the reformer can be used even in an atmosphere with a low oxygen concentration and / or a high steam concentration at high temperatures.
- the remarkable effect of high heat resistance, light weight, low cost and low cost, high reliability and long life is not generated by red oxidation due to steam oxidation on the surface. Plays.
- the fuel reformer according to claim 3 of the present invention is a fuel reformer, comprising: a mixed gas from a fuel supply section for supplying a mixed gas to a charging section for a reforming catalyst, which is in a high-temperature and high-steam-concentration atmosphere in which steam oxidation is likely to occur. Since the Cr oxide layer is previously formed on the surface of the flow path, steam oxidation on this surface is prevented, red scale is prevented from being generated, heat resistance is improved, the weight is reduced, and the cost is reduced. It has a remarkable effect that it is inexpensive, reliable, and has a long life.
- the fuel reformer according to claim 4 of the present invention has a combustion gas flow path side surface in an atmosphere in which water vapor oxidation is likely to occur at high temperature and low oxygen concentration, and steam oxidation easily occurs at high temperature and high steam concentration. Since the Cr oxide layer is previously formed on the surface of the mixed gas flow path from the fuel supply section supplying the mixed gas to the filling section of the reforming catalyst in the atmosphere, the water vapor on these surfaces is formed. Prevents oxidation, prevents red scale from occurring, improves heat resistance, is lightweight, costs less, and is inexpensive It has a remarkable effect of high reliability and long life.
- the Cr oxide layer is formed on the surface of the underlying steel material. It has a remarkable effect that it has good adhesion, is dense and has excellent steam oxidation resistance.
- the Cr material having a higher Cr concentration than the Cr concentration of the base material is formed on the surface of the steel material constituting the reformer by a method such as chroming and chrome plating.
- a method such as chroming and chrome plating.
- the heat treatment temperature can be reduced, and the energy consumption can be reduced without any labor and energy saving.
- the Cr oxide layer formed by the heat treatment becomes denser, and a thin film having a Cr concentration higher than that of the base metal on the surface of the steel material composing the reformer. Since the Cr layer is formed in advance, a remarkable effect is achieved that a dense Cr oxide layer can be formed on the surface in a short time even if the Cr concentration of the base material is low.
- the Cr oxide layer can be easily formed on the surface of the raw steel material before manufacturing the fuel reformer of the present invention, After the Cr oxide layer is formed on the surface of the material, a remarkable effect that the fuel reformer of the present invention can be easily manufactured by assembling or welding using the Cr oxide layer. Is played.
- the fuel reformer composed of the raw steel material on which the Cr oxide layer is not formed is processed to form the Cr oxide on the surface of the raw steel material.
- the production method of claim 9 of the present invention after forming a thin film having a Cr concentration higher than the Cr concentration of the base material on the surface of the raw steel material, it is oxidized at 350 to 65 ° C. Heat treatment in the atmosphere forms a Cr oxide layer, and the reformer is manufactured using the raw steel material on which the Cr oxide layer has been formed.
- the Cr oxide layer formed by heat treatment becomes denser and the surface of the steel material constituting the reformer has a higher Cr concentration than the Cr concentration of the base metal. Since a thin film having a high concentration is formed in advance, there is a remarkable effect that a dense Cr oxide layer can be formed on the surface in a short time even if the Cr concentration of the base material is low.
- a thin film having a Cr concentration higher than that of the base metal is formed on the surface of the raw steel material, and then the raw steel material is used for manufacturing.
- a Cr oxide layer is formed on the surface of the raw steel material, so that no hassle is required. Energy consumption can be reduced and energy savings can be achieved, the Cr oxide layer formed by heat treatment becomes denser, and the Cr concentration of the base metal on the surface of the steel material constituting the reformer 'is improved. Since a thin film having a higher Cr concentration is formed in advance, there is a remarkable effect that a dense Cr oxide layer can be formed on the surface in a short time even if the Cr concentration of the base material is low.
- the present invention relates to a fuel reformer for reforming a hydrocarbon-based fuel into a hydrogen-rich gas and a method for producing the same.
- the surface of the steel material that composes the reformer remains steam even if it is placed in an atmosphere of Z or high steam concentration. It is not oxidized to red scale, has high heat resistance, is lightweight, is inexpensive, inexpensive, has high reliability, has a long service life, and is manufactured according to the present invention. Since the method makes it possible to easily manufacture a low-cost, high-reliability, long-life fuel reformer at a low cost, its industrial value is extremely large.
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/069,912 US6936567B2 (en) | 2000-06-28 | 2001-06-27 | Fuel reformer and manufacturing method of the same |
AU67846/01A AU6784601A (en) | 2000-06-28 | 2001-06-27 | Fuel reforming reactor and method for manufacture thereof |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000194265 | 2000-06-28 | ||
JP2000-194265 | 2000-06-28 |
Publications (1)
Publication Number | Publication Date |
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WO2002000546A1 true WO2002000546A1 (fr) | 2002-01-03 |
Family
ID=18693122
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2001/005528 WO2002000546A1 (fr) | 2000-06-28 | 2001-06-27 | Reacteur de reformage de combustible et son procede de production |
Country Status (3)
Country | Link |
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US (1) | US6936567B2 (ja) |
AU (1) | AU6784601A (ja) |
WO (1) | WO2002000546A1 (ja) |
Cited By (3)
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JP2005272211A (ja) * | 2004-03-25 | 2005-10-06 | Aisin Seiki Co Ltd | 燃料改質器 |
WO2011039468A1 (fr) | 2009-09-30 | 2011-04-07 | Valeo Equipements Electriques Moteur | Agencement de redressement de courant pour machine electrique tournante, notamment alternateur pour vehicule automobile, et machine electrique tournante comportant un tel agencement |
WO2011039480A2 (fr) | 2009-09-30 | 2011-04-07 | Valeo Equipements Electriques Moteur | Machine electrique tournante polyphasee a capot de protection, notamment alternateur pour vehicule automobile |
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US7165393B2 (en) * | 2001-12-03 | 2007-01-23 | Catalytica Energy Systems, Inc. | System and methods for improved emission control of internal combustion engines |
US7082753B2 (en) * | 2001-12-03 | 2006-08-01 | Catalytica Energy Systems, Inc. | System and methods for improved emission control of internal combustion engines using pulsed fuel flow |
EP1563169A1 (en) * | 2002-11-15 | 2005-08-17 | Catalytica Energy Systems, Inc. | Devices and methods for reduction of nox emissions from lean burn engines |
DE602004031845D1 (de) * | 2003-06-10 | 2011-04-28 | Sumitomo Metal Ind | Ng |
US8006484B2 (en) * | 2005-02-14 | 2011-08-30 | Eaton Corporation | Systems and methods for reducing emissions of internal combustion engines using a fuel processor bypass |
JP5428103B2 (ja) * | 2007-02-21 | 2014-02-26 | 国立大学法人 大分大学 | 低温水素製造用触媒及びその製造方法と水素製造方法 |
WO2009036386A1 (en) * | 2007-09-13 | 2009-03-19 | Chellappa Anand S | A method and apparatus for reformation of fuels at low temperatures |
US20170069917A1 (en) * | 2015-09-08 | 2017-03-09 | Institute Of Nuclear Energy Research, Atomic Energy Council, Executive Yuan | Growing method of layers for protecting metal interconnects of solid oxide fuel cells |
JP6624017B2 (ja) * | 2016-11-10 | 2019-12-25 | トヨタ自動車株式会社 | 内燃機関の排気浄化装置 |
DK180247B1 (en) | 2018-11-20 | 2020-09-14 | Blue World Technologies Holding ApS | Fuel cell system, its use and method of its operation |
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Also Published As
Publication number | Publication date |
---|---|
US6936567B2 (en) | 2005-08-30 |
US20020121461A1 (en) | 2002-09-05 |
AU6784601A (en) | 2002-01-08 |
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